Johan Bielecki

Templated Growth of Covalently Bonded Three‐Dimensional Carbon Nanotube Networks Originated from Graphene

A template-assisted method that enables the growth of covalently bonded three-dimensional carbon nanotubes (CNTs) originating from graphene at a large scale is demonstrated. Atomic force microscopy-based mechanical tests show that the covalently bonded CNT structure can effectively distribute external loading throughout the network to improve the mechanical strength of the material.

A statistical model of hydrogen bond networks in liquid alcohols

We here present a statistical model of hydrogen bond induced network structures in liquid alcohols. The model generalises the Andersson-Schulz-Flory chain model to allow also for branched structures. Two bonding probabilities are assigned to each hydroxyl group oxygen, where the first is the probability of a lone pair accepting an H-bond and the second is the probability that given this bond also the second lone pair is bonded. The average hydroxyl group cluster size, cluster size distribution, and the number of branches and leaves in the tree-like network clusters are directly determined from these probabilities. The applicability of the model is tested by comparison to cluster size distributions and bonding probabilities obtained from Monte Carlo simulations of the monoalcohols methanol, propanol, butanol, and propylene glycol monomethyl ether, the di-alcohol propylene glycol, and the tri-alcohol glycerol. We find that the tree model can reproduce the cluster size distributions and the bonding probabilities for both mono- and poly-alcohols, showing the branched nature of the OH-clusters in these liquids. Thus, this statistical model is a useful tool to better understand the structure of network forming hydrogen bonded liquids. The model can be applied to experimental data, allowing the topology of the clusters to be determined from such studies.

Coherent diffraction of single Rice Dwarf virus particles using hard X-rays at the Linac Coherent Light Source

Single particle diffractive imaging data from Rice Dwarf Virus (RDV) were recorded using the Coherent X-ray Imaging (CXI) instrument at the Linac Coherent Light Source (LCLS). RDV was chosen as it is a well-characterized model system, useful for proof-of-principle experiments, system optimization and algorithm development. RDV, an icosahedral virus of about 70 nm in diameter, was aerosolized and injected into the approximately 0.1 μm diameter focused hard X-ray beam at the CXI instrument of LCLS. Diffraction patterns from RDV with signal to 5.9 Ångström were recorded. The diffraction data are available through the Coherent X-ray Imaging Data Bank (CXIDB) as a resource for algorithm development, the contents of which are described here.

Automated identification and classification of single particle serial femtosecond X-ray diffraction data

The first hard X-ray laser, the Linac Coherent Light Source (LCLS), produces 120 shots per second. Particles injected into the X-ray beam are hit randomly and in unknown orientations by the extremely intense X-ray pulses, where the femtosecond-duration X-ray pulses diffract from the sample before the particle structure is significantly changed even though the sample is ultimately destroyed by the deposited X-ray energy. Single particle X-ray diffraction experiments generate data at the FEL repetition rate, resulting in more than 400,000 detector readouts in an hour, the data stream during an experiment contains blank frames mixed with hits on single particles, clusters and contaminants. The diffraction signal is generally weak and it is superimposed on a low but continually fluctuating background signal, originating from photon noise in the beam line and electronic noise from the detector. Meanwhile, explosion of the sample creates fragments with a characteristic signature. Here, we describe methods based on rapid image analysis combined with ion Time-of-Flight (ToF) spectroscopy of the fragments to achieve an efficient, automated and unsupervised sorting of diffraction data. The studies described here form a basis for the development of real-time frame rejection methods, e.g. for the European XFEL, which is expected to produce 100 million pulses per hour.

Transferring the entatic-state principle to copper photochemistry

The entatic state denotes a distorted coordination geometry of a complex from its typical arrangement that generates an improvement to its function. The entatic-state principle has been observed to apply to copper electron-transfer proteins and it results in a lowering of the reorganization energy of the electron-transfer process. It is thus crucial for a multitude of biochemical processes, but its importance to photoactive complexes is unexplored. Here we study a copper complex-with a specifically designed constraining ligand geometry-that exhibits metal-to-ligand charge-transfer state lifetimes that are very short. The guanidine-quinoline ligand used here acts on the bis(chelated) copper(I) centre, allowing only small structural changes after photoexcitation that result in very fast structural dynamics. The data were collected using a multimethod approach that featured time-resolved ultraviolet-visible, infrared and X-ray absorption and optical emission spectroscopy. Through supporting density functional calculations, we deliver a detailed picture of the structural dynamics in the picosecond-to-nanosecond time range.

Two-component heat diffusion observed in LaMnO3 and La0.7Ca0.3MnO3

We investigate the low-temperature electron, lattice, and spin dynamics of LaMnO3 (LMO) and La0.7Ca0.3MnO3 (LCMO) by resonant pump-probe reflectance spectroscopy. Probing the high-spin d-d transition as a function of time delay and probe energy, we compare the responses of the Mott insulator and the double-exchange metal to the photoexcitation. Attempts have previously been made to describe the sub-picosecond dynamics of CMR manganites in terms of a phenomenological three temperature model describing the energy transfer between the electron, lattice and spin subsystems followed by a comparatively slow exponential decay back to the ground state. However, conflicting results have been reported. Here we first show clear evidence of an additional component in the long term relaxation due to film-to-substrate heat diffusion and then develop a modified three temperature model that gives a consistent account for this feature. We confirm our interpretation by using it to deduce the bandgap in LMO. In addition we also model the non-thermal sub-picosecond dynamics, giving a full account of all observed transient features both in the insulating LMO and the metallic LCMO.

Coherent soft X-ray diffraction imaging of coliphage PR772 at the Linac coherent light source

Single-particle diffraction from X-ray Free Electron Lasers offers the potential for molecular structure determination without the need for crystallization. In an effort to further develop the technique, we present a dataset of coherent soft X-ray diffraction images of Coliphage PR772 virus, collected at the Atomic Molecular Optics (AMO) beamline with pnCCD detectors in the LAMP instrument at the Linac Coherent Light Source. The diameter of PR772 ranges from 65–70 nm, which is considerably smaller than the previously reported ~600 nm diameter Mimivirus. This reflects continued progress in XFEL-based single-particle imaging towards the single molecular imaging regime. The data set contains significantly more single particle hits than collected in previous experiments, enabling the development of improved statistical analysis, reconstruction algorithms, and quantitative metrics to determine resolution and self-consistency.

Experimental strategies for imaging bioparticles with femtosecond hard X-ray pulses

Facilitating the very short and intense pulses from an X-ray laser for the purpose of imaging small bioparticles carries the potential for structure determination at atomic resolution without the need for crystallization. In this study, experimental strategies for this idea are explored based on data collected at the Linac Coherent Light Source from 40 nm virus particles injected into a hard X-ray beam.

The effect of alendronate on biomineralization at the bone/implant interface

A recent approach to improve the osseointegration of implants is to utilize local drug administration. The presence of an osteoporosis drug may influence both bone quantity and quality at the bone/implant interface. Despite this, the performance of bone-anchoring implants is traditionally evaluated only by quantitative measurements. In the present study, the osteoporosis drug alendronate (ALN) was administrated from mesoporous titania thin films that were coated onto titanium implants. The effect that the drug had on biomineralization was explored both in vitro using simulated body fluid (SBF) and in vivo in a rat tibia model. The SBF study showed that the apatite formation was completely hindered at a high concentration of ALN (0.1 mg/mL). However, when ALN was administrated from the mesoporous coating the surface became completely covered with apatite. Ex vivo characterization of the bone/implant interface using Raman spectroscopy demonstrated that the presence of ALN enhanced the bone mineralization, and that the chemical signature of newly formed bone in the presence of ALN had a higher resemblance to the pre-existing mature bone than to the bone formed without drug. Taken together, this study demonstrates the importance of evaluating the quality of the formed bone to better understand the performance of implants.

Anharmonic softening of Raman active phonons in iron-pnictides: Estimating the Fe isotope effect due to anharmonic expansion

We present Raman measurements on the iron-pnictide superconductors CeFeAsO1-xFx and NdFeAsO1-xFx. Modeling the Fe-As plane in terms of harmonic and a cubic anharmonic Fe-As interactions, we calculate the temperature dependence of the energy and lifetime of the Raman active Fe B-1g mode and fit to the observed energy shift. The shifts and lifetimes are in good agreement with those measured also in other Raman studies which demonstrate that the phonon spectrum, at least at small wave numbers, is well represented by phonon-phonon interactions without any significant electronic contribution. Even at zero temperature there is a non-negligent effect of interactions on the phonon energy, which for the Fe B-1g mode corresponds to 6 cm(-1) or 3% of the total energy of the mode. We also estimate the anharmonic expansion from Fe (56 -> 54) isotope substitution to Delta a approximate to 5.1 x 10(-4) angstrom and Delta d(Fe-As) approximate to 2.5 x 10(-4) angstrom and the shift of harmonic zero-point fluctuations of bond lengths less than or similar to 3 x 10(-5) angstrom(2), giving a total relative average decrease in electronic hopping integrals of vertical bar delta vertical bar/t less than or similar to 2.0 x 10(-4). For a nonphonon-mediated weak-coupling superconductor this gives an isotope exponent alpha similar to 10(-2). The results pose a serious challenge for any theory of superconductivity in the pnictides that does not include electron-phonon interactions to produce a sizable Fe isotope effect.